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| United States Patent |
5,030,704
|
|
Harris
, et al.
|
July 9, 1991
|
Self polymerizable phenylquinoxalines, their preparation and use in
polyphenylquinoxaline homopolymers and copolymers
Abstract
A polyphenylquinoxaline which consists of 1 to 100 mole percent of
structural elements of the formula (IV)
##STR1##
and of 0-99 mole percent of the following repeat unit of formula (V)
##STR2##
where R is selected from the group consisting of H, an alkyl group, a
carbocyclic aromatic group, a heterocyclic aromatic group, or an alkoxy
group, Ar.sub.1 is a carbocyclic aromatic or heterocyclic aromatic group,
and B is selected from the representative group consisting of:
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are the same or different carbocyclic aromatic
or heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2 ;
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group, a carbocyclic aromatic or
heterocyclic aromatic group. A process for manufacture a self
polymerizable phenylquinoxaline subject to polymerization by aromatic
nucleophilic substitution. The use of these polyphenylquinoxalines and
there copolymers as thermally stable thermal plastics for use in
aerospace, high temperature adhesive, microelectronic and membrane (gas
and molecular separation membrane) application.
| Inventors:
|
Harris; Frank W. (Akron, OH);
Korleski; Joseph E. (Massillon, OH)
|
| Assignee:
|
The University of Akron (Akron, OH)
|
| Appl. No.:
|
368572 |
| Filed:
|
June 20, 1989 |
| Current U.S. Class: |
528/125; 525/471; 525/534; 525/535; 528/126; 528/128; 528/220; 528/222; 528/229 |
| Intern'l Class: |
C08G 073/06 |
| Field of Search: |
528/125,126,128,220,222,229
525/471,534,535
|
References Cited
U.S. Patent Documents
| 3326915 | Jun., 1967 | Jackson et al.
| |
| 3852243 | Dec., 1974 | Hergenrother.
| |
| 3852244 | Dec., 1974 | Heath et al.
| |
| 3956238 | May., 1976 | Heath et al.
| |
| 4125725 | Nov., 1978 | Duffy | 544/353.
|
| 4375536 | Mar., 1983 | Hergenrother | 528/125.
|
| 4788271 | Nov., 1988 | Hergenrother et al. | 528/125.
|
| 4908426 | Mar., 1990 | Hergenrother et al. | 528/125.
|
Other References
Connell et al., "Synthesis of Polyphenylquinoxalines Via Aromatic
Nucleophilic Displacement", Polymer Prep. vol. 29, 1988.
Harris et al., Polymer Prep. vol. 28, 1987.
Connell et al., Polymer Prep., vol. 60, 1989.
Labadie et al., Polymer Prep. vol. 28, 1987.
Bass et al., Polymer Prep. vol. 29, 1988.
Hendrick et al., Macromolecules, vol. 21, 1988.
Labadie et al., Extended Abstracts, vol. 87-2, 1665, 1987.
|
Primary Examiner: Kight, III; John
Assistant Examiner: Acquah; Sam A.
Attorney, Agent or Firm: Oldham & Oldham
Claims
What is claimed is:
1. A polyphenylquinoxaline which consists of 1 to 100 mol percent of
structural elements of the formula (IV)
##STR9##
and of 0-99 mole percent of the folowing repeat unit of formula (V)
##STR10##
where R is selected from the group consisting of H, an alkyl group, a
carbocyclic aromatic group, a heterocyclic aromatic group, or an alkoxy
group, Ar.sub.1 is a carbocyclic aromatic or heterocyclic aromatic group,
and B is selected from the representative group consisting of:
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are the same or different carbocyclic aromatic
or heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2 ;
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group, a carbocyclic aromatic or
heterocyclic aromatic group.
2. A polyphenylquinoxaline according to claim 1 wherein said polymer
comprises 100 mole percent of repeat unit of formula (IV) where R is
selected from the group consisting of H, an alkyl group with between 1 to
16 carbon atoms, a carbocyclic aromatic group, a heterocyclic aromatic
group, or an alkoxy group with between 1 to 8 carbon atoms, Ar.sub.1 a
carbocyclic aromatic or heterocyclic aromatic group, and B is selected
from the representative group consisting of:
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are the same of different a carbocyclic
aromatic or heterocyclic aromatic group and Z is selected from the
representative group consisting of CO, SO or SO.sub.2 ;
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group, a carbocyclic aromatic or
heterocyclic aromatic group.
3. A polyphenylquinoxaline according to claim 1, wherein R is hydrogen.
4. A polyphenylquinoxaline according to claim 1, wherein R is an alkyl
group with between 1 to 16 carbon atoms.
5. A polyphenylquinoxaline according to claim 1, wherein R is an alkoxy
group with between 1 to 8 carbon atoms.
6. A polyphenlyquinoxaline according to claim 1, wherein B is ps
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are independently a carbocyclic aromatic or
heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2.
7. A polyphenylquinoxaline according to claim 1, wherein B is
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar hd 4 l is an aliphatic group, a carbocyclic aromatic or
heterocyclic aromatic group.
8. A polyphenylquinoxaline according to claim 7, wherein Ar.sub.4 is an
aliphatic group with between 1 and 16 carbon atoms.
9. A polyphenylquinoxaline according to claim 1, wherein Ar.sub.1 is
derived from the compounds of formula (IV) selected from the
representative group consisting of hydroquinone (1,4-dihydroxybenzene),
resorcinol (1,3-dihydroxybenzene), or various dihydroxynaphthylenes and
wherein B is derived from the compounds of formula (V) selected from the
representative group consisting of 4,4'--difluorobenzophenone,
4,4'-dinitrobenzophenone, or 4,4'-dichlorobenzophrnone.
10. A polyphenylquinoxaline according to claim 1, wherein Ar.sub.1 is
derived from the compounds of formula (IV) selected from the
representative group consisting of hydroquinone (1,4-dihydroxybenzene),
resorcinol (1,3-dihydroxybenzene), or various dihydroxynaphthylenes and
wherein B is derived from the compounds of formula (V) selected from the
representative group consisting of 4,4'-difluorodiphenvlsulfone,
4,4'-dinitrodiphenylsulfone, or 4,4'-dichlorodiphenylsulfone.
11. A polyphenylquinoxaline which consists of 1 to 50 mole percent of
structural elements of the formula (IV)
##STR11##
and of 99-50 mole percent of the following repeat unit of formula (V)
##STR12##
where R is selected from the group consisting of H, an alkyl group with
between 1 to 16 carbon atoms, a carbocyclic aromatic group, a heterocyclic
aromatic group, or an alkoxy group with between 1 to 8 carbon atoms,
Ar.sub.1 a carbocyclic aromatic or heterocyclic aromatic group, and B is
selected from the representative group consisting of:
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are independently a carbocyclic aromatic or
heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2 ;
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group with between 1 and 16 carbon
atoms, a carbocyclic aromatic or heterocyclic aromatic group.
12. A polyphenylquinoxaline according to claim 11 wherein said polymer
comprises 100 mole percent of repeat unit of formula (IV) where R is
selected from the group consisting of H, an alkyl group with between 1 to
16 carbon atoms, a carbocyclic aromatic group, a heterocyclic aromatic
group, or an alkoxy group with between 1 to 8 carbon atoms, Ar.sub.1 a
carbocyclic aromatic or heterocyclic aromatic group, and B is selected
from the representative group consisting of:
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are independently a carbocyclic aromatic or
heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2 ;
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group with between 1 and 16 carbon
atoms, a carbocyclic aromatic or heterocyclic aromatic group.
13. A polyphenylquinoxaline according to claim 11, wherein R is hydrogen.
14. A polyphenylquinoxaline according to claim 11, wherein R is an alkyl
group with between 1 to 16 carbon atoms.
15. A polyphenylquinoxaline according to claim 1, wherein R is an alkoxy
group with between 1 to 8 carbon atoms.
16. A polyphenlyquinoxaline according to claim 10, wherein B is
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are independently a carbocyclic aromatic or
heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2.
17. A polyphenylquinoxaline according to claim 10, wherein B is
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group with between 1 and 16 carbon
atoms, a carbocyclic aromatic or heterocyclic aromatic group.
18. A polyphenylquinoxaline which consists of 51 to 100 mole percent of
structural elements of the formula (IV)
##STR13##
and of 49-0 mole percent of the following repeat unit of formula (V)
##STR14##
where R is selected from the group consisting of H, an alkyl group with
between 1 to 16 carbon atoms, a carbocyclic aromatic group, a heterocyclic
aromatic group, or an alkoxy group with between 1 to 8 carbon atoms,
Ar.sub.1 a carbocyclic aromatic or heterocyclic aromatic group, and B is
selected from the representative group consisting of:
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are independently a carbocyclic aromatic or
heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2 ;
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group with between 1 and 16 carbon
atoms, a carbocyclic aromatic or heterocyclic aromatic group.
19. A polyphenylquinoxaline according to claim 18, wherein said polymer
comprises 100 mole percent of repeat unit of formula (IV) where R is
selected from the group consisting of H, an alkyl group with between 1 to
16 carbon atoms, a carbocyclic aromatic group, a heterocyclic aromatic
group, or an alkoxy group with between 1 to 8 carbon atoms, Ar.sub.1 a
carbocyclic aromatic or heterocyclic aromatic group, and B is selected
from the representative group consisting of:
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are independently a carbocyclic aromatic or
heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2 ;
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group with between 1 and 16 carbon
atoms, a carbocyclic aromatic or heterocyclic aromatic group.
20. A polyphenylquinoxaline according to claim 18, wherein R is hydrogen.
21. A polyphenlyquinoxaline according to claim 18, wherein B is
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are independently a carbocyclic aromatic or
heterocyclic aromatic group and Z is selected from the representative
group consisting of CO, SO or SO.sub.2.
22. A polyphenylquinoxaline according to claim 18, wherein B is
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group with between 1 and 16 carbon
atoms, a carbocyclic aromatic or heterocyclic aromatic group.
23. A process for preparing a self polymerizable phenylquinoxaline of
formula (I) which comprises steps of:
mixing a diamine of the formula (II) with a benzil of formula (III) in a
chlorinated hydrocarbon containing a small amount of an acid catalyst; and
heating the mixture to afford a self polymerizable phenylquinoxaline of
formula (I).
24. A phenylquinoxaline process according to claim 23, wherein the diamine
is 4-fluoro-1,2-diaminobenzene.
25. A phenylquinoxaline process according to claim 23, wherein the benzil
is 4-hydroxy-benzil.
26. A phenylquinoxaline process according to claim 23, wherein the acid
catalyst is selected from the representative group consisting of
trifluoroacetic acid, para-toluenesulfonic acid, or trichloroacetic acid.
Description
TECHNICAL FIELD
This invention describes the manufacture of self polymerizable
phenylquinoxalines and their use in the preparation of
polyphenylquinoxalines and copolymers containing of self polymerizable
phenylquinoxalines monomer.
The present invention relates to new polyquinoxaline homopolymers and
copolymers, their use as thermoplastic in aerospace, microelectronics and
membrane application such as gas separation membranes and molecular
separation membranes and a process for manufacturing 2,3-diaryl
substituted-6-fluoro-quinoxalines where at least one of the aryl groups is
hydroxylated.
Polyquinoxalines, herein sometimes referred to as PPQ's, are a well
established class of high performance thermoplastics with proven potential
in aerospace, microelectronics and membrane applications.
BACKGROUND ART
PPQ's are normally prepared by the reacting of bis-alpha-carbonyl compounds
with an organic tetramine. In U.S. Pat. Nos. 3,852,244 and 3,956,238,
Heath et al., has disclosed the formation of polyether quinoxalines from a
wide variety of polyether bis-alpha-carbonyl compounds and aromatic
organic tetramines.
In "Synthesis of poly(phenylyquinoxaline) with High Glass Transition
Temperatures," Polymer Prep, 28, 71 (1987), Harris et al. has described
the synthesis of various bis(phenylglyoxalyl) napthalenes and their use in
the preparation of PPQ's.
In "The Synthesis and Characterization of Phenolic Hydroxyl Terminated
Polyphenylquinoxaline Oligomers," Polymer Prep, 28, 69 (1987), Labadie et
al. has described the preparation of hydroxy terminated polyphenyl
quinoxalines.
In U.S. Pat. No. 3,326,915, Jackson et al. described the preparation and
use of various self-polymerizable benzopyrazin or quinoxalines, but these
self-polmerizable monomers are polymerized by the same classical
procedures as described in Heath et al. above.
More recently, Connell et al. described in "Synthesis of
Polyphenylquinoxalines via Aromatic Nucleophilic Displacement," Polymer
Prep, 29, 172 (1988), the formation of PPQ's by reacting
bis-hydroxyphenylquinoxalines with an activated difluoro monomers under
aromatic nucleophilic substitution reaction conditions.
Hedrick et al. have also described in "Synthesis of Poly(aryl
ether-phenylquinoxaline)" Proceedings from Polymeric Material Science &
Engineering, 59, 42 (1988), the formation of PPQ's by reacting
bis-fluoro-polyphenylated-quinoxalines with various bis-hydroxylated
aromatic compounds under aromatic nucleophilic substitution reaction
conditions.
However, the aromatic nucleophilic substitution process for making PPQ's
still requires the purification and use of two independent components.
Thus, it appears desirable to manufacture a self polymerization quinoxaline
which polymerizes under aromatic nucleophilic substitute reaction
conditions to yield PPQ's and copolymers containing PPQ's incorporating
the self polymerizable phenylquinoxalines. These PPQ and PPQ copolymers
especially PPQ copolymers containing polyether-ether-ketone, sometimes
referred herein as PEEK, repeat units or PPQ copolymers containing
polyethersulfone, sometimes herein referred to as PES, repeat units have
excellent thermal and mechanical properties and are ideally suited as
useful thermoplastic in the areas of aerospace, high temperature adhesive,
microelectronic and membrane applications. These copolymers have
properties that are tunable to make high temperature thermoplastics,
highly crystalline thermoplastics, lowly crystalline thermoplastics,
organic soluble thermoplastics or organic insoluble thermoplastics.
DISCLOSURE OF THE INVENTION
It is an object of this invention to provide novel, self polymerizable,
phenylquinoxalines incorporating within the same chemical structure an
aromatic nucleophilic displacable group and a group which can displace the
displacable group.
It is a further object of this invention to provide novel PPQ's prepared by
polymerizing the self polymerizable phenylquinoxalines.
A further object of this invention is to provide novel PPQ copolymers based
on the self polymerizable phenylquinoxalines and at lesat one other
systems which can undergo aromatic nucleophilic substitution
polymerization.
A further object of this invention is to provide a usable process for the
manufacturing of 2,3-diaryl-6-fluoro-quinoxalines where at least one aryl
group is hydroxylated.
The novel self polymerizable quinoxalines have the following formula (I):
##STR3##
where Y is selected from the group consisting of F, Cl or NO.sub.2 and Y
is in either the 6 or 7 position of the quinoxaline ring system and where
R is selected from the group consisting of H, an alkyl group having
usually 1 to 16 carbon atoms, a carbocyclic aromatic group, a heterocyclic
aromatic group, or an alkoxy group having usually 1 to 8 carbon atoms.
The phenylquinoxalines of formula (I) can be manufactured according to the
following reaction scheme:
##STR4##
where Y and R are as previously defined. Thus, a representative compound
of formula (II), 4-fluoro-1,2-diaminobenzene, is reacted with a
representative compound of formula (III), 4-hydroxybenzil, in the presence
of a chlorinated hydrocarbon solvent such as chloroform in the presence of
an strong organic acid catalyst such as trifluoroacetic acid,
para-toluenesulfonic acid, or trichloroacetic acid.
The phenylquinoxalines of this invention can be used as monomers for the
manufacture of PPQ's and as monomers for manufacturing copolymers
containing PPQ's and other monomer systems which undergo aromatic
nucleophilic substitution polymerization which consist of 1-100 mole
percent and preferrably from about 10 to 100 mole percent of repeat unit
of formula (IV)
##STR5##
and 0-99 mole percent and preferrably from about 90 to 0 mole precent of
repeat unit formula (V)
##STR6##
where R is as previously defined, Ar.sub.1 is a carbocyclic aromatic or
heterocyclic aromatic group, and B is selected from the representative
group consisting of:
Ar.sub.2 --Z--Ar.sub.3 (i)
where Ar.sub.2 and Ar.sub.3 are the same or different a carbocyclic
aromatic or heterocyclic aromatic group and Z is selected from the
representative group consisting of CO, SO or SO.sub.2
Z'--Ar.sub.4 --Z' (ii)
where Z' is an activated carbocyclic aromatic or heterocyclic aromatic
group and Ar.sub.4 is an aliphatic group having usually 1 and 16 carbon
atoms, a carbocyclic aromatic or heterocyclic aromatic group.
Repeat units of formula (V) can be made by the following reaction scheme:
##STR7##
where Y, Ar.sub.1 and B are as previously defined. Thus, an dihydroxyaryl
compound of formula (VI) such as hydroquinone (1,4-dihydroxybenzene),
resorcinol (1,3-dihydroxybenzene), or various dihydroxynaphthylenes is
reacted with a disubstituted B linked aryl compound such as
4,4'-difluorobenzophenone, 4,4'-difluorodiphenylsulfone,
4,4'-difluorodiphenylsulfoxide, 4,4'-dinitrobenzophenone,
4,4'-dinitrodiphenylsulfone, or 4,4'-dichlorobenzophenone.
The polymerization reaction is carried out under standard aromatic
nucleophilic reaction conditions which involve mixing the monomers
together in an appropriate organic solvent with excess of K.sub.2 CO.sub.3
as proton absorption component and removing the water as it is formed in
the case of the above described copolymers.
BEST MODE FOR CARRYING OUT THIS INVENTION
Applicants have found that the PPQ's derived from phenylquinoxalines of
formula (I) or copolymers having at least 1 mole percent of repeat units
derived from self polymerizable phenylquinoxaline of formula (I) represent
a new and novel class of thermoplastic PPQ's. The PPQ's and copolymers of
this invention are formed using a nuclephilic substitution action from a
self polymerizable phenylquinoxaline which has an active leaving group
such as fluorine, chlorine or nitro, displacable by a nucleophilic site on
the same molecule usually an aromatic hydroxy group where the quinoxaline
ring system serves as an activating group. These polymers are important
because of their excellent thermo-mechanical properties and the mild
conditions under which they are formed.
In preparing the homo PPQ's, a solution of the self polymerizing
phenylquinoxaline of formula (I) is dissolved in a mixture of
N-methylpyrollodone (NMP) and toluene to afford monomer solubility
containing an excess of K.sub.2 CO.sub.3 which absorbs the protonic acid
generated during aromatic nucleophilic substitution under nitrogen. The
polymer is formed as a fibrious componenet which can be dissolved in
chlorinated hydrocarbons and reprecipitated from methanol. Although the
self polymerizable phenylquinoxalines of formula (I) can have the leaving
group Y substituted in the sixth or seventh position of the
phenylquinoxaline ring system, the pure components, that is those that
have either all six substituted leaving groups or seven substituted
leaving groups, can be used as the self polymerizing monomer.
The use of these pure components results in homo PPQ's which have greater
order and a rigidity and as well PPQ copolymers with these same enhanced
properties. Copolymers using self polymerizable phenylquinoxalines of
formula (I) in a mole percent greater than or equal to 1, involve reacting
the phenylquinoxaline of formula (I) with preferrably a near 1:1 mixture
of an activated disubstituted aromatic component where the substituents
are nucleophilic substitution leaving groups such as fluorine, chlorine or
nitro and an aromatic diol where the diols are directly attached to an
aromatic ring such as 1,4-di-hydroxy benzene. Small excess of either the
aromatic diols or the disubstituted aromatic compounds are acceptable with
the excess usually ranging from about 1 to 10% by weight.
These copolymers are useful in applications where the phenylquinoxaline
structure increases the polymers thermal stability and imparts a different
morphology to the polymer which can improve the polymers rigidity and
packing efficiency resulting in improved fiber forming properties and more
durable film or reinforcing agents for molecular composities.
Copolymers consisting of 51-100 mole percent of repeat units of formula
(IV) and 49-0 mole percent of repeat units of formula (V) are particularly
preferred for applications where the thermoplastic character of the PPQ
block predominate the characteristic of the copolymer. This application
include most of the standard applications that PPQ's are traditionally
used for in industry. However, the incorporation of upto 49 mole percent
of repeat units of formula (V) will allow modifications of the PPQ normal
physical properties to accomplish polymers tailors made for a given
application.
Copolymer consisting of 1-50 mole percent of repeat units of formula (IV)
and 99-50 mole percent of repeat units of formula (V) represent the other
side of the spectrum of copolymers, that is copolymers where the block
incorporating repeat units of formula (V) predominate. These copolymers
will express more of the native homopolymer characteristics of homopolymer
consisting of 100 mole percent of repeat units of formula (V). However,
the inclusion of at least 1 mole percent of repeat units of formula (IV)
will allow wide latitude in the design of particular polymers for a given
application.
The copolymers which incorporate PEEK blocks show a variation in copolymer
properties as the amount of PEEK [poly(ether-ether ketones] content is
increased. In the 25 to 50 mole present of PEEK block incorporated in the
the copolymer a shift in the copolymers final properties in that the
T.sub.g increases from a T.sub.g platuea that dominates the copolymers
from 50 to 90 percent PEEK composition.
In the case of PPQ-PEEK copolymers, the compounds of formula (VI) which are
particularly preferred are selected from the illustrative and
representative group consisting of hydroquinone (1,4-dihydroxybenzene),
resorcinol (1,3-dihydroxybenzene), or various dihydroxynaphthylenes; while
the particularly preferred compounds of formula (V) are selected from the
illustrative and representative group consisting of
4,4'-difluorobenzophenone, 4,4'-dinitrobenzophenone, or
4,4'-dichlorobenzophenone.
The incorporation of PES (polyethersulfone) on the other hand only causes a
steedy increase in the T.sub.g of the copolymers as the mole percent is
increased from 25 to 75%.
In the case of PPQ-PES copolymers, the compounds of formula (VI) which are
particularly preferred are selected from the illustrative and
representative group consisting of hydroquinone (1,4-dihydroxybenzene),
resorcinol (1,3-dihydroxybenzene), or various dihydroxynaphthylenes; while
the particularly preferred compounds of formula (V) are selected from the
illustrative and representative group consisting of
4,4'-difluorodiphenylsulfone, 4,4'-dinitrodiphenylsulfone or
4,4'-dichlorodiphenylsulfone.
Other dihydroxy compound of formula (IV) include
4,5-bis(4-hydroxyphenyl)-2-phenylimidazole. Other difluoro compounds of
formula (V) are selected from the illustrative and representative group
consisting of 1,3-bis(4-fluorobenzoyl)benzene,
1,4-bis(4-fluorobenzoyl)benzene, 4,4'-bis(4-fluorobenzoyl)diphenylether,
4,4'-bis (4-fluorobenzoyl)diphenylmethane,
4,4'-bis(4-fluorobenzoyl)diphenylsulfone,
2,6-bis(4-fluorobenzoyl)naphthalene or 4,4'-bis(4-fluorobenzoyl)biphenyl.
The invention will be better understood by reference to the following
examples which are included for the purpose of illustration and not
limitation.
EXAMPLE 1
Preparation of Self-Polymerizable Phenylouinoxalines
This example illustrates the preparation of a near 50-50 mixture of
2-phenyl-3-(4-hydroxyphenyl)-6-fluoroquinoxaline and
2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline.
To a one liter round-bottomed flask equipped with an overhead stirrer and a
reflux condensor was added 73.12 grams (0.323 moles) of 4-hydroxybenzil,
40.77 grams (0.323 moles) of 4-fluoro-1,2-diaminobenzene and 500 mls of
chloroform. After 5 drops of trifluoroacetic acid was added, the solution
was stirred and heated at reflux for 5 hrs. The solution was allowed to
cool to room temperature, extracted with 300 mls of water, and dried over
MgSO.sub.4. After the solvent was removed under reduced pressure, the
residue was recrystallized 3 times from 95% ethanol to yield 92.97 grams
(91%) of a bright yellow powder formula (Ia):
##STR8##
Compound (Ia) had the following physical properties:
mp=82.degree.-117.degree. C.; IR (KBr) 1600 cm.sub.-1 quinoxaline
absorption, 3123 cm.sub.-1 OH absorption; .sup.1 H-NMR (CDCl.sub.3) 6.6
ppm (s, 1H, OH) and 7.3-8.3 ppm (m, 12H, aromatic). Anal. Calcd. C.sub.20
H.sub.13 FN.sub.2 O: C, 75.94; H 4.14. Actual: C, 76.04; H, 4.20.
EXAMPLE 2
Homopolymerization
This example illustrates the preparation of a PPQ homopolymer based on the
self polymerizable phenylquinoxaline of formula (Ia) prepared in Example
1.
25 grams (0.079 moles) of monomer (Ia) from example 1 was dissolved in 200
mls of a 50:50 (v/v) solutions of NMP/toluene containing excess K.sub.2
O.sub.3 under nitrogen. The mixture was stirred for 4 hrs at 160.degree.
C. during which time the water of condensation was collected in a Dean
Stark trap. The toluene was then removed as the mixture was heated to
190.degree. C. for 1 hr. The temperature was then raised to 202.degree. C.
for an additional hr. The dark red mixture was diluted with 200 mls NMP
and added to 2000 mls of a stirred 75:25 (v/v) solution of methanol/acetic
acid. The fibrous white PPQ was collected by filtration, dissolved in
chloroform and filtered. The polymer was reprecipitated into methanol and
in refluxing water; and then dried at 150.degree. C. under reduced
pressure for 18 hrs.
The homopolymer was obtained as a white fibrous material which displayed
the following properties: [n]=1.23 dl/g, T.sub.g =247.degree. C., and TGA
(5% weight loss) 555.degree. D. (N.sub.2) and 565.degree. C. (air), and
was soluble in NMP, DMAc, m-cresol, and chlorinated hydrocarbons.
A thin film (3 mil) of the homopolymer was cast from NMP and subjected to
preliminary stress-strain measurements according to ASTM D882. The tensile
strength of the film was 107.+-.6 MPa (15,515 PSI) and its tensile modulus
was 3.18.+-.0.15 GPa (461,100 PSI).
A sample of the homopolymer was compression molded at 300.degree. C. and
1000 PSI. Preliminary measurements on the molded specimen gave a flexural
modulus of 2.8.+-.0.3 MPa and G.sub.1C =0.68.+-.0.11 N-m/m.sup.2.
EXAMPLE 3
This example illustrates the preparation of a PPQ homopolymer based on
either a pure 2-phenyl-3-(4-hydroxyphenyl) -6-fluoro-quinoxaline or pure
2-(4-hydroxyphenyl) -3-phenyl-6-fluoro-quinoxaline.
25 grams (0.079 moles) of 2-(4-hydroxy phenyl)-3
-phenyl-6-fluoroquinoxaline from example 1 is dissolved in 200 mls of a
50:50 (v/v) solutions of NMP/toluene containing excess K.sub.2 O.sub.3
under nitrogen. The mixture is stirred for 4 hrs at 160.degree. C. during
which time the water of condensation is collected in a Dean Stark trap.
The toluene is then removed as the mixture is heated to 190.degree. C. for
1 hr. The temperature is then raised to 202.degree. C. for an additional
hr. The dark red mixture is diluted with 200 mls NMP and added to 2000 mls
of a stirred 75:25 (v/v) solution of methanol/acetic acid. The fibrous
white PPQ is collected by filtration, dissolved in chloroform and
filtered. The polymer is reprecipitated into methanol and in refluxing
water; and then dried at 150.degree. C. under reduced pressure for 18 hrs.
PREPARATION OF PPO-PEEK CO-POLYMERS
EXAMPLE 4
This example illustrates the preparation of a PPQ-PEEK copolymer consisting
of 75 mole percent of a PPQ repeat unit of formula (II) based on the self
polymerizable phenylquinoxalines of formula (Ia), prepared in Example 1,
and 25 mole percent of a PEEK repeat unit of formula (III) based on the
reaction of hydroquinone and 4,4'-difluorobenzophenone.
18.75 grams (0.0593 moles) of self polymerizable phenylquinoxaline (Ia)
from example 1, 1.07 grams (0.0099 moles) of hydroquinone, and 2.155 grams
(0.0099 moles) of 4,4'-difluorobenzophenone were dissolved in 200 mls of a
50:50 (v/v) solutions of NMP/toluene containing excess K.sub.2 CO.sub.3
under nitrogen. The mixture was stirred for 4 hrs at 160.degree. C. during
which time the water of condensation was collected in a Dean Stark trap.
The toluene was then removed as the mixture was heated to 190.degree. C.
for 1 hr. The temperature was then raised to 202.degree. C. for an
additional hr. The dark red mixture was diluted with 200 mls NMP and added
to 2000 mls of a stirred 75:25 (v/v) solution of methanol/acetic acid. The
fibrous white PPQ-PEEK copolymer was collected by filtration, dissolved in
chloroform and filtered. The polymer was reprecipitated into methanol and
in refluxing water; and then dried at 150.degree. C. under reduced
pressure for 18 hrs.
The homopolymer was obtained as a white fibrous material which displayed
the following properties: [n]=0.81 dl/g in m-cresol at 30.1.degree. C.,
and T.sub.g =222.degree. C.
EXAMPLE 5
This example illustrates the preparation of a PPQ-PEEK copolymer consistinq
of 50 mole percent of a PPQ repeat units of formula (II) based on the self
polymerizable phenylquinoxalines of formula (Ia), prepared in Example 1,
and 50 mole percent of a PEEK repeat unit of formula (III) based on the
reaction between hydroquinone and 4,4'-difluorobenzophenone.
12.5 grams (0.0395 moles) of self polymerizable phenylquinoxaline (Ia) from
example 1, 2.175 grams (0.0198 moles) of hydroquinone, and 4.309 grams
(0.0198 moles) of 4,4'-difluorobenzophenone were dissolved in 200 mls of a
50:50 (v/v) solutions of NMP/toluene containing excess K.sub.2 CO.sub.3
under nitrogen. The mixture was stirred for 4 hrs at 160.degree. C. during
which time the water of condensation was collected in a Dean Stark trap.
The toluene was then removed as the mixture was heated to 190.degree. C.
for 1 hr. The temperature was then raised to 202.degree. C. for an
additional hr. The dark red mixture was diluted with 200 mls NMP and added
to 2000 mls of a stirred 75:25 (v/v) solution of methanol/acetic acid. The
fibrous white PPQ-PEEK copolymer was collected by filtration, dissolved in
chloroform and filtered. The polymer was reprecipitated into methanol and
in refluxing water; and then dried at 150.degree. C. under reduced
pressure for 18 hrs.
The homopolymer was obtained as a white fibrous material which displayed
the following properties: [n]=1.19 dl/g in m-cresol at 30.1.degree. C. and
T.sub.g =170.degree. C.
EXAMPLE 6
This example illustrates the preparation of a PPQ-PEEK copolymer consisting
of 25 mole percent of a PPQ repeat units of formula (II) based on the self
polymerizable phenylquinoxalines of formula (Ia), prepared in Example 1,
and 75 mole percent of a PEEK repeat unit of formula (III) based on the
reaction between hydroquinone and 4,4'-difluorobenzophenone.
6.25 grams (0.0198 moles) of self polymerizable phenylquinoxaline (Ia) from
example 1, 3.262 grams (0.0296 moles) of hydroquinone, and 6.464 grams
(0.0296 moles) of 4,4'-difluorobenzophenone were dissolved in 200 mls of a
50:50 (v/v) solutions of NMP/toluene containing excess K.sub.2 CO.sub.3
under nitrogen. The mixture was stirred for 4 hrs at 160.degree. C. during
which time the water of condensation was collected in a Dean Stark trap.
The toluene was then removed as the mixture was heated to 190.degree. C.
for 1 hr. The temperature was then raised to 202.degree. C. for an
additional hr. The dark red mixture was diluted with 200 mls NMP and added
to 2000 mls of a stirred 75:25 (v/v) solution of methanol/acetic acid. The
fibrous white PPQ-PEEK copolymer was collected by filtration, dissolved in
chloroform and filtered. The polymer was reprecipitated into methanol and
in refluxing water; and then dried at 150.degree. C. under reduced
pressure for 18 hrs.
The homopolymer was obtained as a white fibrous material which displayed
the following properties: [n]=1.08 dl/g in conc. H.sub.2 SO.sub.4 at
30.1.degree. C. and T.sub.g =170.degree. C.
EXAMPLE 7
This example illustrates the preparation of a PPQ-PEEK copolymer consisting
of 10 mole percent of a PPQ repeat units of formula (II) based on the self
polymerizable phenylquinoxalines of formula (Ia), prepared in Example 1,
and 90 mole percent of a PEEK repeat unit of formula (III) based on the
reaction between hydroquinone and 4,4'-difluorobenzophenone.
2.5 grams (0.0079 moles) of self polymerizable phenylquinoxaline (Ia) from
example 1, 3.914 grams (0.0356 moles) of hydroquinone, and 7.757 grams
(0.0356 moles) of 4,4'-difluorobenzophenone were dissolved in 200 mls of a
50:50 (v/v) solutions of NMP/toluene containing excess K.sub.2 CO.sub.3
under nitrogen. The mixture was stirred for 4 hrs at 160.degree. C. during
which time the water of condensation was collected in a Dean Stark trap.
The toluene was then removed as the mixture was heated to 190.degree. C.
for 1 hr. The temperature was then raised to 202.degree. C. for an
additional hr. The dark red mixture was diluted with 200 mls NMP and added
to 2000 mls of a stirred 75:25 (v/v) solution of methanol/acetic acid. The
fibrous white PPQ-PEEK copolymer was collected by filtration, dissolved in
chloroform and filtered. The polymer was reprecipitated into methanol and
in refluxing water; and then dried at 150.degree. C. under reduced
pressure for 18 hrs.
The homopolymer was obtained as a white fibrous material which displayed
the following properties: [n]=0.37 dl/g in conc. H.sub.2 SO.sub.4 at
30.1.degree. C., T.sub.g =165.degree. C., and T.sub.m =320.degree. C.
PREPARATION OF PPO-PES CO-POLYMERS
EXAMPLE 8
This example illustrates the preparation of a PPQ-PES copolymer consisting
of 75 mole percent of a PPQ repeat unit of formula (II) based on the self
polymerizable phenylquinoxalines of formula (Ia), prepared in Example 1,
and 25 mole percent of a PES repeat unit of formula (III) based on the
reaction of hydroquinone and 4,4'-difluorodiphenylsulfone.
18.75 grams (0.0593 moles) of self polymerizable phenylquinoxaline (Ia)
from example 1, 1.087 grams (0.0099 moles) of hydroquinone, and 2.511
grams (0.0099 moles) of 4,4'-difluorodiphenylsulfone were dissolved in 200
mls of a 0:50 (v/v) solutions of NMP/toluene containing excess K.sub.2
CO.sub.3 under nitrogen. The mixture was stirred for 4 hrs at 160.degree.
C. during which time the water of condensation was collected in a Dean
Stark trap. The toluene was then removed as the mixture was heated to
190.degree. C. for 1 hr. The temperature was then raised to 202.degree. C.
for an additional hr. The dark red mixture was diluted with 200 mls NMP
and added to 2000 mls of a stirred 75:25 (v/v) solution of methanol/acetic
acid. The fibrous white PPQ-PES copolymer was collected by filtration,
dissolved in chloroform and filtered. The polymer was reprecipitated into
methanol and in refluxing water; and then dried at 150.degree. C. under
reduced pressure for 18 hrs.
The homopolymer was obtained as a white fibrous material which displayed
the following properties: [n]=1.06 dl/g in m-cresol at 30.1.degree. C. and
T.sub.g =240.degree. C.
EXAMPLE 9
This example illustrates the preparation of a PPQ-PES copolymer consisting
of 50 mole percent of a PPQ repeat units of formula (II) based on the self
polymerizable phenylquinoxalines of formula (Ia), prepared in Example 1,
and 50 mole percent of a PES repeat unit of formula (III) based on the
reaction between hydroquinone and 4,4'-difluorodiphenylsulfone.
12.5 grams (0.0395 moles) of self polymerizable phenylquinoxaline (Ia) from
example 1, 2.175 grams (0.0198 moles) of hydroquinone, and 5.022 grams
(0.0198 moles) of 4,4'-difluorodiphenylsulfone were dissolved in 200 mls
of a 50:50 (v/v) solutions of NMP/toluene containing excess K.sub.2
CO.sub.3 under nitrogen. The mixture was stirred for 4 hrs at 160.degree.
C. during which time the water of condensation was collected in a Dean
Stark trap. The toluene was then removed as the mixture was heated to
190.degree. C. for 1 hr. The temperature was then raised to 202.degree. C.
for an additional hr. The dark red mixture was diluted with 200 mls NMP
and added to 2000 mls of a stirred 75:25 (v/v) solution of methanol/acetic
acid. The fibrous white PPQ-PES copolymer was collected by filtration,
dissolved in chloroform and filtered. The polymer was reprecipitated into
methanol and in refluxing water; and then dried at 150.degree. C. under
reduced pressure for 18 hrs.
The homopolymer was obtained as a white fibrous material which displayed
the following properties: [n]=1.16 dl/g in m-cresol at 30.1.degree. C. and
T.sub.g =232.degree. C.
EXAMPLE 10
This example illustrates the preparation of a PPQ-PES copolymer consisting
of 25 mole percent of a PPQ repeat units of formula (II) based on the self
polymerizable phenylquinoxalines of formula (Ia), prepared in Example 1,
and 75 mole percent of a PES repeat unit of formula (III) based on the
reaction between hydroquinone and 4,4'-difluorodiphenylsulfone.
6.25 grams (0.0198 moles) of self polymerizable phenylquinoxaline (Ia) from
example 1, 3.262 grams (0.0296 moles) of hydroquinone, and 7.532 grams
(0.0296 moles) of 4,4'-difluorodiphenylsulfone were dissolved in 200 mls
of a 50:50 (v/v) solutions of NMP/toluene containing excess K.sub.2
CO.sub.3 under nitrogen. The mixture was stirred for 4 hrs at 160.degree.
C. during which time the water of condensation was collected in a Dean
Stark trap. The toluene was then removed as the mixture was heated to
190.degree. C. for 1 hr. The temperature was then raised to 202.degree. C.
for an additional hr. The dark red mixture was diluted with 200 mls NMP
and added to 2000 mls of a stirred 75:25 (v/v) solution of methanol/acetic
acid. The fibrous white PPQ-PES copolymer was collected by filtration,
dissolved in chloroform and filtered. The polymer was reprecipitated into
methanol and in refluxing water; and then dried at 150.degree. C. under
reduced pressure for 18 hrs.
The homopolymer was obtained as a white fibrous material which displayed
the following properties: [n]=1.08 dl/g in H.sub.2 SO.sub.4 at
30.1.degree. C. and T.sub.g =219.degree. C.
All of the PEEK and PES copolymers of examples 4-10 had decomposition
temperatures (temperature until a 5% weight loss occurs in the TGA
spectra) between 500 and 565.degree. C. in nitrogen and between
505.degree. and 550.degree. C. in air.
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